System And Method For Liquid Hydrocarbon Desulfurization

ABSTRACT

A liquid hydrocarbon desulfurization system having at least one processing unit, and preferably an initial and an end processing unit. Each processing unit having a reactor assembly and a sorption system. An aqueous system directs aqueous into the reactor assembly together with liquid hydrocarbon, wherein the two are mixed using shear mixers. An adsorbent system provides adsorbent to the sorption column to adsorb the oxidized sulfur resulting through the mixing of the liquid hydrocarbon with the aqueous. A system having multiple processing units is disclosed, as well as systems for transferring adsorbent and providing aqueous. A plurality of methods is likewise disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from U.S. Pat. App. Ser. No. 62/623,562filed Jan. 30, 2018, entitled “System and Method for Liquid HydrocarbonDesulfurization,” the entire disclosure of which is hereby incorporatedby reference in its entirety.

This application is related to, but does not claim priority from, U.S.Pat. App. Ser. No. 62/471,159 filed Mar. 14, 2017, entitled “System andMethod for Liquid Hydrocarbon Desulfurization” and U.S. Pat. App. Ser.No. 62/524,816 filed Jun. 26, 2017, entitled “System and Method forLiquid Hydrocarbon Desulfurization”, the entire disclosure of each ofthe foregoing application is incorporated herein by reference in theirentirety.

BACKGROUND OF THE DISCLOSURE 1. Field of the Disclosure

The disclosure relates in general to liquid hydrocarbon desulfurization,and more particularly, to a system and method for the oxidation ofsulfur compounds in liquid hydrocarbons.

2. Background Art

Environmental concerns continue to increase with the increased use ofhydrocarbon fuels, and have increased considerably with the use of thesefuels in areas of the world where environmental regulations may not beas advanced as there are in other global locations.

One pollutant of hydrocarbon fuels is Sulfur, generally found in organiccompounds such as thiophenes. Once combusted it becomes oxidized, that,when present in the atmosphere, has several deleterious effects. One ofthese effects is being a component of acid rain. Traditionally, thesulfur content of liquid hydrocarbons has been reduced byhydro-desulfurization, a process that requires relatively hightemperatures and pressures in the presence of hydrogen gas to functioneconomically. However, this technology is relatively costly, timeconsuming and expensive, which, in turn, limits the ability to rapidlyassist countries in reducing Sulfur emissions.

Other methods have been developed for desulfurization. One of which isoxidative desulfurization, and another is bio oxidation. There are alsodrawbacks with these processes; overall they are promising. Among otherdrawbacks with oxidative desulfurization, it is difficult to efficientlyuse the reagents used during the oxidation step. The oxidizer isconsumed in the reaction, and is quite costly. While in some systems,the oxidizer can be recycled, it remains difficult. Furthermore, thereare operational issues associated with its implementation.

While the prior art is replete with patents directed to oxidativedesulfurization, it has remained difficult to develop industrialprocesses for such innovations. Among other such prior art patents areU.S. Pat. No. 3,163,593 issued to Webster; U.S. Pat. No. 8,574,428issued to Schucker; U.S. Pat. No. 7,758,745 issued to Cheng; U.S. Pat.No. 7,314,545 issued to Karas; U.S. Pat. No. 7,774,749 issued toMartinie; U.S. Pat. No. 6,596,914 issued to Gore; PCT Pub. No.WO2013/051202 published to Ellis and EP. App. Pub NO. 0482841 issued toCollins. Each of the foregoing patents is incorporated herein in itsentirety.

SUMMARY OF THE DISCLOSURE

The disclosure is directed in one aspect of the disclosure to a methodof desulfurizing a liquid hydrocarbon. The method comprises the stepsof: providing an initial processing unit and an end processing unit, theinitial processing unit having an initial reactor assembly and aninitial sorption system, the end processing unit having an end reactorassembly, a separator and an end sorption system; feeding a liquidhydrocarbon having a sulfur content into the initial reactor assembly;feeding an aqueous feed into the initial reactor assembly; shear mixingthe liquid hydrocarbon and the aqueous feed within the initial reactorassembly, to, in turn, react the aqueous feed with the sulfur content ofthe liquid hydrocarbon; directing the liquid hydrocarbon and aqueousfeed to the initial sorption system; feeding a sorbent into the initialsorption system; adsorbing at least some of the sulfur content that hasreacted with the aqueous feed from the liquid hydrocarbon; directingliquid hydrocarbon from the initial sorption system to the end reactorassembly; directing the aqueous feed from the initial sorption system tothe end reactor assembly; shear mixing the liquid hydrocarbon and theaqueous feed within the end reactor assembly, to, in turn, react theaqueous feed with the sulfur content of the liquid hydrocarbon;directing the liquid hydrocarbon and the aqueous feed to the separator;separating the liquid hydrocarbon and the aqueous feed from each otherin the separator; directing the liquid hydrocarbon from the separator tothe end sorption system; feeding a sorbent into the end sorption system;adsorbing at least some of the sulfur content that has reacted with theaqueous feed from the liquid hydrocarbon; and removing the liquidhydrocarbon.

In some configurations, the method further comprises the step ofproviding additional aqueous feed to the end reactor assembly one ofbefore or during the step of shear mixing in the end reactor assembly.

In some configurations, the method further includes the step of feedinga sorbent into the initial sorption system further comprises the stepof: removing the sorbent from the end sorption system; and feeding theremoved sorbent from the end sorption system to the initial sorptionsystem.

In some configurations, the steps of removing and feeding occur atpredetermined intervals.

In some configurations, the liquid hydrocarbon travels through thesystem substantially continuously.

In some configurations, the method includes the step of heating theliquid hydrocarbon within the initial sorption system.

In some configurations, the aqueous feed comprises an organic acid, anoxidizer, a strong acid.

In some configurations, the organic acid is selected from the groupconsisting of: acetic, formic, benzoic, or other acid of the carboxylicfamily, as well as mixtures of the same.

In some configurations, the oxidizer comprises one of the groupconsisting of: peroxide, such as hydrogen peroxide or an organicperoxide, such as meta-chloroperoxybenzoic acid, or a solid oxidizersuch as Oxone.

In some configurations, the strong acid comprises one of the groupconsisting of: sulfuric acid and nitric acid.

In some configurations, the sorbent comprises an activated aluminasorbent.

In another aspect of the disclosure, the disclosure is directed to amethod of desulfurizing a liquid hydrocarbon. The method comprises thesteps of: providing an initial processing unit and an end processingunit, and at least one middle processing unit therebetween, the initialprocessing unit having an initial reactor assembly and an initialsorption system, the end processing unit having an end reactor assembly,a separator and an end sorption system, and the at least one middleprocessing unit having a middle reactor assembly and a middle sorptionsystem; feeding a liquid hydrocarbon having a sulfur content into theinitial reactor assembly; feeding an aqueous feed into the initialreactor assembly; shear mixing the liquid hydrocarbon and the aqueousfeed within the initial reactor assembly, to, in turn, react the aqueousfeed with the sulfur content of the liquid hydrocarbon; directing theliquid hydrocarbon and aqueous feed to the initial sorption system;feeding a sorbent into the initial sorption system; adsorbing at leastsome of the sulfur content that has reacted with the aqueous feed fromthe liquid hydrocarbon; directing liquid hydrocarbon from the initialsorption system to the at least one middle reactor; directing theaqueous feed from the initial sorption system to the at least one middlereactor; feeding a sorbent into the at least one middle reactor;adsorbing at least some of the sulfur content that has reacted with theaqueous feed from the liquid hydrocarbon; directing liquid hydrocarbonfrom the at least one middle sorption system to the end reactorassembly; directing the aqueous feed from the at least one middlesorption system to the end reactor assembly; shear mixing the liquidhydrocarbon and the aqueous feed within the end reactor assembly, to, inturn, react the aqueous feed with the sulfur content of the liquidhydrocarbon; directing the liquid hydrocarbon and the aqueous feed tothe separator; separating the liquid hydrocarbon and the aqueous feedfrom each other in the separator; directing the liquid hydrocarbon fromthe separator to the end sorption system; feeding a sorbent into the endsorption system; adsorbing at least some of the sulfur content that hasreacted with the aqueous feed from the liquid hydrocarbon; and removingthe liquid hydrocarbon.

In some configurations, the method includes the step of providingadditional aqueous feed to at least one of the at least one middlereactor assembly one of before or during the step of shear mixing in theat least one middle reactor assembly.

In some configurations, the liquid hydrocarbon proceeds sequentiallyfrom the initial processing unit to the at least one middle processingunit to the end processing unit, while the sorbent proceeds sequentiallyfrom the end processing unit, to the at least one middle processing unitto the initial processing unit.

In some configurations, the sulfur content of the liquid hydrocarbon atthe initial processing unit is at least 100 ppm and more preferably atleast 1500 ppm, and the sulfur content of the liquid hydrocarbon afterthe end sorption system is below 15 ppm and more preferably below 2 ppm.

In some configurations, the at least one middle processing unitcomprises at least two middle processing units positioned sequentiallybetween the initial processing unit and the end processing unit.

In some configurations, the method further comprises the step of heatingthe liquid hydrocarbon in at least one of the middle sorption systems.

In some configurations, the liquid hydrocarbon is heated to between 40°C. and 95° C., and more preferably to approximately 85° C.

In yet another aspect of the disclosure, the disclosure is directed to asystem of liquid hydrocarbon desulfurizing. The system includes aninitial processing unit and an end processing unit. The initialprocessing unit having a reactor assembly and a sorption system. Thereactor assembly including a reactor vessel and a recirculatory systemstructurally configured to recirculate fluid within the reactor vessel.The sorption system having an inlet in fluid communication with thereactor assembly, an inlet for absorbent, and at least one hydrocarbonoutlet. The end processing unit having an end reactor, a separator andan end sorption system. The end reactor assembly includes an end reactorvessel and an end recirculatory system structurally configured torecirculate fluid within the end reactor vessel. The separator is influid communication with the end reactor assembly. The separator has anoutlet for liquid hydrocarbon and an outlet for an aqueous feed. The endsorption system has an inlet in fluid communication with the outlet forliquid hydrocarbon, an inlet for absorbent and an outlet for liquidhydrocarbon. The at least one hydrocarbon outlet of the sorption systemis coupled to the end reactor assembly so as to be in fluidcommunication therewith.

In some configurations, the end sorption system has an outlet forabsorbent, which is in fluid communication with the inlet for absorbentof the sorption system of the initial processing unit.

In some configurations, the sorption system includes a heater and theend sorption system includes a heater, the heater structurallyconfigured to raise the temperature of the liquid hydrocarbontherewithin.

In some configurations, the system further includes at least one endprocessing unit. The end processing unit has at least one middleprocessing unit having a reactor assembly including a reactor vessel anda recirculatory system structurally configured to recirculate fluidwithin the reactor vessel, and a sorption system having an inlet influid communication with the reactor assembly, an inlet for absorbent,and at least one hydrocarbon outlet. The at least one middle processingunit is positioned between the initial processing unit and the endprocessing unit.

In some configurations, at least one middle processing unit comprises atleast two middle processing units positioned sequentially and betweenthe initial processing unit and the end processing unit.

In some configurations, the recirculatory system of at least one of theinitial processing unit and the end processing unit includes a shearmixer.

In some configurations, a flow of liquid hydrocarbon proceeds from theinitial processing unit to the end processing unit and a flow ofadsorbent proceeds from the end processing unit to the initialprocessing unit.

In some configurations, the system is structurally configured tocontinuously direct a flow of liquid hydrocarbon from the initialprocessing unit to the end processing unit.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosure will now be described with reference to the drawingswherein:

FIG. 1 of the drawings is a schematic representation of adesulfurization system showing five processing units; and

FIG. 2 of the drawings is a schematic representation of a singleprocessor unit taken of the desulfurization system.

DETAILED DESCRIPTION OF THE DISCLOSURE

While this disclosure is susceptible of embodiment in many differentforms, there is shown in the drawings and described herein in detail aspecific embodiment(s) with the understanding that the presentdisclosure is to be considered as an exemplification and is not intendedto be limited to the embodiment(s) illustrated.

It will be understood that like or analogous elements and/or components,referred to herein, may be identified throughout the drawings by likereference characters. In addition, it will be understood that thedrawings are merely schematic representations of the invention, and someof the components may have been distorted from actual scale for purposesof pictorial clarity.

Referring now to the drawings and in particular to FIG. 1, liquidhydrocarbon desulfurization system is shown generally at 10. Thedesulfurization system is configured to remove sulfur content fromliquid hydrocarbons, such as, for example, kerosene, diesel, fuel oil,jet fuel, gasoline, among others. The system is not limited to use withany particular type of liquid hydrocarbon. Additionally, it iscontemplated that the system can lower the sulfur content to below 15ppm, to for example 2 ppm, or less. Often times, the startinghydrocarbon has a sulfur content that can be 1500 or higher, while thesystem is contemplated for use with starting liquid hydrocarbon that isin excess of 15 ppm, and generally in excess of 100 ppm, 200 ppm, 300ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, and onupwards of 1500 ppm or greater. Again, the system is not limited to usewith any particular hydrocarbon, or a hydrocarbon with any particularsulfur content.

The processing unit utilizes an aqueous feed. The aqueous feed maycomprise any number of different formulations. In some configurations,the aqueous feed may comprise an organic acid, an oxidizer, a strongacid and, optionally, an ionic liquid. The particular ratios can bevaried depending on the particular fuel type and the compositionthereof. The organic acid may comprise any one of the following, withoutlimitation, acetic, formic, benzoic, or other acid of the carboxylicfamily, as well as mixtures of the same. The oxidizer may includeperoxide which can be hydrogen peroxide or an organic peroxide, such asmeta-chloroperoxybenzoic acid, or a solid oxidizer such as Oxone. Thestrong acid can be either sulfuric or nitric. The foregoing are notexhaustive, but are illustrative examples. The disclosure is not limitedto these particular acids. Additionally, it is contemplated that anionic liquid may be fully omitted from some configurations.Additionally, the processing unit utilizes an activated aluminaadsorbent. It is further contemplated that liquid adsorbents can beutilized with the system.

The desulfurization system includes a processing unit, such asprocessing unit 12, aqueous system 18 and transfer system 19. It will beunderstood that the system is shown with five processing units, while itis contemplated that a greater or lesser number of processor units maybe required to achieve the desired reduction of sulfur content from theliquid hydrocarbon. In the configuration shown, there is an initialprocessing unit 14, and an end processing unit 16, with three processingunits 12 therebetween. The system is configured for continuousdesulfurization of liquid hydrocarbons, while it is contemplated thatthe system can be adapted to a batch process. It is contemplated thatthe system disclosed can process at a rate of 10 gallons per minute andcan reduce the sulfur content from approximately 1500 ppm to less than15 ppm. Of course, the system can be scaled larger or smaller, and canbe configured to have different reductions in sulfur content, as well asdifferent starting sulfur content and ending content. Additionally, thesystem can be configured to handle a number of other liquid hydrocarbonswhich may require variation to the system.

With additional reference to FIG. 2, the processing units 12 includereactor assembly 20 and sorption system 22. The reactor assembly 20includes reactor vessel 30, recirculatory 32 and outfeed 34. The reactorvessel comprises fuel infeed 35 and an aqueous infeed 36. In theconfiguration shown, the reactor vessel comprises a vessel having acapacity of 193 gallons. The recirculatory comprises a pump 38 and ashear mixer 37. The recirculatory takes fluid from the reactor vesseland circulates the same back through the reactor vessel by direction ofthe pump. The fluid is directed through the shear mixer duringcirculation. In the configuration shown, the shear mixer may be a shearplate of the type disclosed in U.S. Pat. No. 8,192,073 entitled “MixingApparatus and Method for Manufacturing an Emulsified Fuel” issued Jun.5, 2012, the entire disclosure of which is incorporated herein byreference in its entirety. The outfeed 34 from the reactor assembly 20comprises a bleed valve 39 which can be configured to maintain aparticular amount of fluid within the reactor vessel 30.

The sorption system is shown as comprising sorption column 40 and heater(or cooler in some configurations) 46 positioned within the sorptioncolumn. It is desired that the heater maintains the liquid hydrocarbonat an elevated temperature as compared to ambient. In the configurationshown, the heater is configured to maintain a temperature ofapproximately 85° C. within the sorption column. It is contemplated thatdepending on the hydrocarbon, the aqueous feed, the transfer system andthe sulfur content, among other considerations, the temperature may bedesired to be higher or lower than the 85° C. set forth above, forexample, at a temperature of between 40° C. and 95° C., while higher andlower temperatures are contemplated. The sorption column 40 includesfuel/aqueous inlet 41, fuel/aqueous outlet 42, adsorbent inlet 44 andadsorbent outlet 45.

As will be discussed in greater detail with respect to the operation ofthe system, the fuel infeed 35 and the aqueous infeed 36 may meet priorto entry into the reactor vessel 30, such that a single inlet ispresented to the reactor vessel. A gear pump 31 (or other pump) may beutilized to direct fuel into the infeed, and a reagent pump 33 (or otherpump) may be utilized to direct aqueous to the aqueous infeed 36. Ashear mixer 37′ may be presented between the joining of the fuel andaqueous infeed and prior to the entry thereof into the reactor vessel.

The recirculatory recirculates fluid at a desired rate. The bleed valve39 is controlled to direct the outflow therethrough so as to maintain adesired volume of liquid hydrocarbon within the reactor vessel. Theoutfeed 34 is directed to the fuel/aqueous inlet 41 of the sorptioncolumn 40. The fuel/aqueous outlet 42 is positioned on the opposite endof the fuel/aqueous inlet 41 so as to allow the fluid to pass from oneend through the other (and beyond the adsorbent that is positionedwithin the sorption column). The fuel/aqueous outlet is coupled to thesubsequent reactor assembly, and in particular to the fuel and aqueousinfeed thereof.

It will be understood that a constant flow rate can be directed into thefuel infeed and the aqueous infeed, and the bleed valve can control thevolume of liquid hydrocarbon within the reactor vessel, and at a flowrate direct liquid hydrocarbon to the sorption column, such that thesystem runs continuously.

With reference to FIG. 1, and FIG. 2, the initial processing unit 14, isconfigured much like that of the remaining processing units, however,there is typically a heater such as heater 24 (FIG. 1) which ispositioned prior to the fuel infeed so as to heat the fuel fromgenerally ambient to the desired elevated temperature (in theconfiguration shown, 85° C.).

Similarly, the end processing unit is configured much like that of theremaining processing units, however, and with reference to FIG. 1, thereis typically a separator 26 and a cooler 28 coupled thereto. Theseparator is configured to separate aqueous from fuel and is positionedbetween the reactor assembly and the sorption system of that processingunit. The separator 26 includes infeed 50, fuel outlet 52 and aqueousoutlet 54. The infeed 50 receives fuel/aqueous from the reactor vessel,and the fuel outlet 52 is directed to the sorption system 22. In theconfiguration shown, cooler 28 is positioned on the fuel outlet betweenthe separator 26 and the sorption column. The aqueous outlet is directedto the aqueous system. The sorption system of the end processing unitdoes not typically include a heater, rather the cooler is used to returnthe temperature of the liquid hydrocarbon back to or toward ambienttemperature. In some configurations, the separator may be omittedwherein a reagent dosages at the end processing unit have different(i.e., lower) requirements.

The aqueous system 18 is shown in FIG. 1 as including aqueous feed mixer60 and aqueous feed makeup 62. The aqueous feed mixer includes inlet 66,outlet 68 and pump 69. The inlet includes recirculation, and may beconnected to another tank for receiving further new aqueous. The outletof the aqueous feed mixer is coupled to the aqueous infeed of the endprocessing unit 16. Additional aqueous can be added to the aqueous feedmixer (or to the aqueous feed makeup.

The aqueous feed makeup 62 includes separator inlet 70, reactor inlet72, outlet 74 and pump 76. The separator inlet 70 is coupled to theaqueous outlet 54 of the separator. The reactor outlet 72 is coupled tothe outlet and/or inlet of the aqueous feed mixer so as to selectivelydirect aqueous to the aqueous infeed of the end processing unit. Theoutlet 74 of the aqueous feed makeup 62 is directed to the aqueousinfeed of each of the remaining reactor vessels, including that of theinitial processing unit, and the processing units between the initialprocessing unit and the end processing unit. A pump may be positionedinline to provide the aqueous to the aqueous infeed of the remainingprocessing units. It will be understood that reagent pumps may bepositioned between the aqueous infeed and the pump to properly meter theaqueous as necessitated or desired.

The transfer system 19 is shown in FIGS. 1 and 2, collectively, ascomprising adsorbent supply inlet 80 and adsorbent transfer system 82.The adsorbent supply inlet 80 is directed to the adsorbent inlet of theend processing unit. The adsorbent transfer system 82 includes, at eachof the processing units, jet pump 84 and motive fluid system 86. Withreference to FIG. 2, the jet pump 84 includes outlet 87, motive fluidinlet 88 and adsorbent inlet 89. The jet pump functions using theventure principle so as to direct adsorbent from within the respectivesorption system through the adsorbent outlet 45 of the sorption column,into the adsorbent inlet 89, while directing motive fluid from themotive fluid system into the motive fluid inlet 88 to pull the solidabsorbent from within the sorption system. The pulled solid adsorbentand the motive fluid is then directed into the adsorbent inlet of apreceding processing unit, with the exception of the initial processingunit. In the case of the initial processing unit, the pulled solidadsorbent and the motive fluid is then directed to the alumina supplyoutlet 81.

The motive fluid system 86 includes motive fluid tank 90 and motivefluid pump 92. The motive fluid tank includes motive fluid outlet 94 andmotive fluid inlet 96. Motive fluid can additionally be provided throughvalve 101, whose flowrate can be controlled by orifice 102. The motivefluid provides the driving fluid that creates the vacuum to pull thesolid adsorbent from within the sorption column through the adsorbentoutlet of the sorption column. In the configuration contemplated, themotive fluid comprises a liquid hydrocarbon. Preferably, the motivefluid has a sulfur content that is lower than that of the fluid enteringthe desulfurization system, and preferably at, near or lower than thatof the desired output sulfur level after processing by the system. Itwill be understood that the transfer system shown in the configurationdescribed is merely one configuration. One of skill in the art couldenvision other such systems, such as those use impeller pumps, as wellas other structures and equipment to effectuate movement of thematerial.

In operation, the system is started up. Initially, a number of differentmechanisms can be utilized to reach an initial steady state operation.In particular, the system may start with adsorbent in each of thesorption columns, the heaters turned on to the desired temperature andthe desired aqueous feed being directed to each of the processing units.It will be understood that the starting conditions can be achievedthrough a number of different processes, methods and steps.

Once initiated, eventually a steady state operation is achieved. In theconfiguration shown, the fuel infeed to the initial processing unit isset at a desired rate. At such a rate, and with a liquid hydrocarbonwherein the sulfur content is known, the appropriate amount of aqueousthat is to be directed into each reactor assembly can be determinedthrough calculation. Additionally, with the known feed rate, the bleedvalves of each of the processing units can be controlled to maintain acertain level of liquid hydrocarbon within each of the reactor vessels.

From here, we can describe the movement of each of the three movingliquids and solids through the system. Namely, this includes the liquidhydrocarbon, aqueous and adsorbent. The liquid hydrocarbon is proceedingthrough the processing units, sequentially, from the initial processingunit to the end processing unit. The aqueous proceeds through thereactor assembly by proceeding to the reactor vessel of the endprocessing unit, and from there being distributed (with any requiredmakeup or additional aqueous) to each of the processing units prior tothe end processing unit substantially simultaneously. The adsorbentproceeds to the sorption column of the end processing unit, and is movedsequentially from the end processing unit, to the initial processingunit before being removed for stripping.

In greater detail, the liquid hydrocarbon is introduced into the fuelinfeed of the reactor vessel of the initial processing unit. It is mixedwith aqueous and introduced into the reactor vessel of the initialprocessing unit. It is circulated by the recirculatory, wherein the mixof the aqueous and the liquid hydrocarbon is achieved by the shearmixers. The introduction is continuous as is the recirculation. It iscontemplated that on average, in the configuration shown, the mixture isrecirculated within the reactor vessel for approximately fifteen minutes(again, exemplary and not to be deemed a limiting time ofrecirculation). The bleed valve directs the liquid hydrocarbon and theaqueous mixture into the sorption column of the initial processing unitthrough the fuel/aqueous inlet. The mixture is pushed through theadsorbent wherein the oxidized sulfur is adsorbed and the reagent areabsorbed. The absorbed aqueous allows for continued oxidation to occurin the sorbent bed formed by the adsorbent (alumina in the configurationshown). The liquid hydrocarbon and aqueous proceeds through the fueloutlet and into the fuel infeed of the subsequent processing unit.Additional aqueous is provided through the infeed.

The process repeats with each subsequent processing unit. At the endprocessing unit, initially, the liquid hydrocarbon and aqueous isdirected into the reactor vessel of the end processing unit, withadditional aqueous added. As with the prior units, the mixture isrecirculated and directed through shear mixers. The bleed valve directsthe liquid hydrocarbon and aqueous mixture into the separator 26. At theseparator, the aqueous is separated from the liquid hydrocarbon, and theaqueous (that was injected into the reactor vessel of the end processingunity by reagent pump 103 is removed through the aqueous outlet andtransmitted to the aqueous feed makeup. The liquid hydrocarbon is thendirected into the sorption column and through the fuel/aqueous inlet(although at this point there should be little to no aqueous mixed withthe liquid hydrocarbon). The liquid hydrocarbon is directed beyond theadsorbent and out of the fuel/aqueous outlet of the sorption column ofthe end processing unit. At this point, the liquid hydrocarbon isgenerally free of any aqueous, a substantial majority of the sulfur hasbeen oxidized, and the liquid hydrocarbon is ready for utilization. Inthe configuration shown, sulfur content can be reduced below 15 ppm.

The adsorbent has a generally reverse movement from the end processingunit to the initial processing unit. That is, once steady stateoperation is achieved, the adsorbent in each of the processing units isremoved therefrom through the adsorbent transfer system, and directedinto the immediately preceding sorption column through the adsorbentinlet. The adsorbent in the initial processing unit is removed and sentthrough the adsorbent supply outlet for stripping or for disposal. Freshand/or stripped adsorbent is directed from the adsorbent supply inletthrough the adsorbent inlet of the sorption column and into the sorptioncolumn of the end processing unit. This process, in the configurationshown, is not a continuous process, but is repeated at predeterminedtime intervals. In the configuration shown, the adsorbent is cycledaccording to the above process every four hours. It is contemplated thatthe time interval may be altered from the four hours and the four hoursis merely exemplary. The cycle may repeat multiple times in an hour, oras few as only ever several hours or days. The cycle is repeated basedupon a number of factors, including, but not limited to the sulfurcontent, the flow rates, the adsorbent used, the particular hydrocarbon,the nature of the sulfur content, the type of aqueous utilized, amongother considerations. It is further contemplated that the process may bedone continuously as well.

It will be understood that in some applications only two or threeprocessing units will be required, whereas in other configurations inexcess of five may be required. Wherein processing occurs at a 10gallon/minute rate of a liquid hydrocarbon having 1500 ppm, the systemis sized so as to occupy the space of approximately two shippingcontainers. Of course, this is merely exemplary and it is contemplatedthat the system can be scaled smaller or larger, and can accommodatedifferent liquid hydrocarbons, at different flow rates, with differentsulfur content, as well as different adsorbent and different aqueous.

The foregoing description merely explains and illustrates the disclosureand the disclosure is not limited thereto except insofar as the appendedclaims are so limited, as those skilled in the art who have thedisclosure before them will be able to make modifications withoutdeparting from the scope of the disclosure.

What is claimed is:
 1. A method of desulfurizing a liquid hydrocarbon,comprising the steps of: providing an initial processing unit and an endprocessing unit, the initial processing unit having an initial reactorassembly and an initial sorption system, the end processing unit havingan end reactor assembly, a separator and an end sorption system; feedinga liquid hydrocarbon having a sulfur content into the initial reactorassembly; feeding an aqueous feed into the initial reactor assembly;shear mixing the liquid hydrocarbon and the aqueous feed within theinitial reactor assembly, to, in turn, react the aqueous feed with thesulfur content of the liquid hydrocarbon; directing the liquidhydrocarbon and aqueous feed to the initial sorption system; feeding asorbent into the initial sorption system; adsorbing at least some of thesulfur content that has reacted with the aqueous feed from the liquidhydrocarbon; directing liquid hydrocarbon from the initial sorptionsystem to the end reactor assembly; directing the aqueous feed from theinitial sorption system to the end reactor assembly; shear mixing theliquid hydrocarbon and the aqueous feed within the end reactor assembly,to, in turn, react the aqueous feed with the sulfur content of theliquid hydrocarbon; directing the liquid hydrocarbon and the aqueousfeed to the separator; separating the liquid hydrocarbon and the aqueousfeed from each other in the separator; directing the liquid hydrocarbonfrom the separator to the end sorption system; feeding a sorbent intothe end sorption system; adsorbing at least some of the sulfur contentthat has reacted with the aqueous feed from the liquid hydrocarbon; andremoving the liquid hydrocarbon.
 2. The method of claim 1 furthercomprising the step of: providing additional aqueous feed to the endreactor assembly one of before or during the step of shear mixing in theend reactor assembly.
 3. The method of claim 1 wherein the step offeeding a sorbent into the initial sorption system further comprises thestep of: removing the sorbent from the end sorption system; and feedingthe removed sorbent from the end sorption system to the initial sorptionsystem.
 4. The method of claim 3, wherein the steps of removing andfeeding occur at predetermined intervals.
 5. The method of claim 4wherein the liquid hydrocarbon travels through the system substantiallycontinuously.
 6. The method of claim 1 further comprising the step ofheating the liquid hydrocarbon within the initial sorption system. 7.The method of claim 1 wherein the aqueous feed comprises an organicacid, an oxidizer, a strong acid.
 8. The method of claim 7 wherein theorganic acid is selected from the group consisting of: acetic, formic,benzoic, or other acid of the carboxylic family, as well as mixtures ofthe same.
 9. The method of claim 7 wherein the oxidizer comprises one ofthe group consisting of: a peroxide, such as hydrogen peroxide or anorganic peroxide, such as meta-chloroperoxybenzoic acid, or a solidoxidizer such as Oxone.
 10. The method of claim 7 wherein the strongacid comprises one of the group consisting of: sulfuric acid and nitricacid.
 11. The method of claim 1 wherein the sorbent comprises anactivated alumina sorbent.
 12. A method of desulfurizing a liquidhydrocarbon, comprising the steps of: providing an initial processingunit and an end processing unit, and at least one middle processing unittherebetween, the initial processing unit having an initial reactorassembly and an initial sorption system, the end processing unit havingan end reactor assembly, a separator and an end sorption system, and theat least one middle processing unit having a middle reactor assembly anda middle sorption system; feeding a liquid hydrocarbon having a sulfurcontent into the initial reactor assembly; feeding an aqueous feed intothe initial reactor assembly; shear mixing the liquid hydrocarbon andthe aqueous feed within the initial reactor assembly, to, in turn, reactthe aqueous feed with the sulfur content of the liquid hydrocarbon;directing the liquid hydrocarbon and aqueous feed to the initialsorption system; feeding a sorbent into the initial sorption system;adsorbing at least some of the sulfur content that has reacted with theaqueous feed from the liquid hydrocarbon; directing liquid hydrocarbonfrom the initial sorption system to the at least one middle reactor;directing the aqueous feed from the initial sorption system to the atleast one middle reactor; feeding a sorbent into the at least one middlereactor; adsorbing at least some of the sulfur content that has reactedwith the aqueous feed from the liquid hydrocarbon; directing liquidhydrocarbon from the at least one middle sorption system to the endreactor assembly; directing the aqueous feed from the at least onemiddle sorption system to the end reactor assembly; shear mixing theliquid hydrocarbon and the aqueous feed within the end reactor assembly,to, in turn, react the aqueous feed with the sulfur content of theliquid hydrocarbon; directing the liquid hydrocarbon and the aqueousfeed to the separator; separating the liquid hydrocarbon and the aqueousfeed from each other in the separator; directing the liquid hydrocarbonfrom the separator to the end sorption system; feeding a sorbent intothe end sorption system; adsorbing at least some of the sulfur contentthat has reacted with the aqueous feed from the liquid hydrocarbon; andremoving the liquid hydrocarbon.
 13. The method of claim 12 whereinfurther comprising the step of: providing additional aqueous feed to atleast one of the at least one middle reactor assembly one of before orduring the step of shear mixing in the at least one middle reactorassembly.
 14. The method of claim 12 wherein the liquid hydrocarbonproceeds sequentially from the initial processing unit to the at leastone middle processing unit to the end processing unit, while the sorbentproceeds sequentially from the end processing unit, to the at least onemiddle processing unit to the initial processing unit.
 15. The method ofclaim 12 wherein the sulfur content of the liquid hydrocarbon at theinitial processing unit is at least 100 ppm and more preferably at least1500 ppm, and the sulfur content of the liquid hydrocarbon after the endsorption system is below 15 ppm and more preferably below 2 ppm.
 16. Themethod of claim 12 wherein the at least one middle processing unitcomprises at least two middle processing units positioned sequentiallybetween the initial processing unit and the end processing unit.
 17. Themethod of claim 12 further comprising the step of heating the liquidhydrocarbon in at least one of the middle sorption systems.
 18. Themethod of claim 17 wherein the liquid hydrocarbon is heated to between40° C. and 95° C., and more preferably to approximately 85° C.
 19. Asystem for liquid hydrocarbon desulfurizing comprising: an initialprocessing unit, the initial processing unit having a reactor assemblyincluding a reactor vessel and a recirculatory system structurallyconfigured to recirculate fluid within the reactor vessel; a sorptionsystem having an inlet in fluid communication with the reactor assembly,an inlet for absorbent, and at least one hydrocarbon outlet; an endprocessing unit, the end processing unit having an end reactor assemblyincluding an end reactor vessel and an end recirculatory systemstructurally configured to recirculate fluid within the end reactorvessel; a separator in fluid communication with the end reactorassembly, the separator having an outlet for liquid hydrocarbon and anoutlet for an aqueous feed; and an end sorption system having an inletin fluid communication with the outlet for liquid hydrocarbon, an inletfor absorbent and an outlet for liquid hydrocarbon, wherein the at leastone hydrocarbon outlet of the sorption system is coupled to the endreactor assembly so as to be in fluid communication therewith.
 20. Thesystem of claim 19 wherein the end sorption system has an outlet forabsorbent, which is in fluid communication with the inlet for absorbentof the sorption system of the initial processing unit.
 21. The system ofclaim 19 wherein the sorption system includes a heater and the endsorption system includes a heater, the heater structurally configured toraise the temperature of the liquid hydrocarbon therewithin.
 22. Thesystem of claim 19 further comprising at least one middle processingunit having a reactor assembly including a reactor vessel and arecirculatory system structurally configured to recirculate fluid withinthe reactor vessel, and a sorption system having an inlet in fluidcommunication with the reactor assembly, an inlet for absorbent, and atleast one hydrocarbon outlet, the at least one middle processing unitbeing positioned between the initial processing unit and the endprocessing unit.
 23. The system of claim 22 wherein at least one middleprocessing unit comprises at least two middle processing unitspositioned sequentially and between the initial processing unit and theend processing unit.
 24. The system of claim 19 wherein therecirculatory system of at least one of the initial processing unit andthe end processing unit includes a shear mixer.
 25. The system of claim19 wherein a flow of liquid hydrocarbon proceeds from the initialprocessing unit to the end processing unit and a flow of adsorbentproceeds from the end processing unit to the initial processing unit.26. The system of claim 19 wherein the system is structurally configuredto continuously direct a flow of liquid hydrocarbon from the initialprocessing unit to the end processing unit.